CN111440271A - Maleic anhydride grafted polyolefin wax, hot-melt pressure-sensitive adhesive modified by using same, and preparation method and application of hot-melt pressure-sensitive adhesive - Google Patents
Maleic anhydride grafted polyolefin wax, hot-melt pressure-sensitive adhesive modified by using same, and preparation method and application of hot-melt pressure-sensitive adhesive Download PDFInfo
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- CN111440271A CN111440271A CN202010286850.8A CN202010286850A CN111440271A CN 111440271 A CN111440271 A CN 111440271A CN 202010286850 A CN202010286850 A CN 202010286850A CN 111440271 A CN111440271 A CN 111440271A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/02—Copolymers of mineral oil hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of hot-melt pressure-sensitive adhesives, in particular to a maleic anhydride grafted polyolefin wax, a hot-melt pressure-sensitive adhesive modified by the same, and a preparation method and application of the hot-melt pressure-sensitive adhesive. The maleic anhydride grafted polyolefin wax is mainly prepared from the following raw materials in parts by weight: 85-90 parts of metallocene polyolefin wax, 1-6 parts of maleic anhydride, 0.1-0.8 part of initiator, 5-15 parts of plasticizer, 0-1 part of antioxidant and 0.5-2 parts of active auxiliary monomer. When the prepared maleic anhydride grafted polyolefin wax is used for preparing the hot-melt pressure-sensitive adhesive, the prepared hot-melt pressure-sensitive adhesive has excellent processing mobile phase, obviously enhances the peeling strength of a base material, slightly increases the annular initial adhesion, widens the application range of the hot-melt pressure-sensitive adhesive, and can be widely used for bonding materials such as plastics, metals, fibers, leatherware and the like.
Description
Technical Field
The invention relates to the technical field of hot-melt pressure-sensitive adhesives, in particular to a maleic anhydride grafted polyolefin wax, a hot-melt pressure-sensitive adhesive modified by the same, and a preparation method and application of the hot-melt pressure-sensitive adhesive.
Background
Hot Melt Pressure Sensitive Adhesive (HMPSA) is significantly tacky at room temperature and can directly adhere to an adherend by deforming itself under slight pressure. The HMPSA has the advantages of environmental protection, rapid on-line coating, no need of a post-drying process, high production efficiency, excellent bonding performance and the like, and has wide development prospect.
The main components of the hot-melt pressure-sensitive adhesive comprise a thermoplastic elastomer, tackifying resin, a plasticizer, an antioxidant and the like. In the main component, the common thermoplastic elastomer has low molecular polarity, relatively low bonding strength to a base material and narrow adaptability range of the base material.
Based on this, the skilled person functionalizes the thermoplastic elastomer to increase the adhesion of the pressure sensitive adhesive to the polar substrate, but the functionalized thermoplastic elastomer has too large molecular weight to affect the processing flow property and the wetting effect on the substrate, resulting in insignificant effect.
Patent application CN103102454A proposes a method for preparing maleic anhydride grafted polyolefin wax by coating initiator microcapsules with wax, so as to make the reaction system uniform and avoid side reactions caused by over-excitation of the reaction, but the preparation process of the microcapsules is complicated, and volatile organic solvent is used, which is not environment-friendly.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide maleic anhydride-grafted polyolefin wax, which solves the technical problems of many side reactions and unstable polyolefin molecular chains in the prior art.
A second object of the present invention is to provide a method for preparing maleic anhydride-grafted polyolefin wax, which is simple to operate, mild in conditions, less in side reactions, and environmentally friendly.
A third object of the present invention is to provide a hot-melt pressure-sensitive adhesive having good processing fluidity and excellent adhesive strength.
The fourth purpose of the invention is to provide a preparation method of the hot-melt pressure-sensitive adhesive, which is simple in process and easy to operate.
The fifth purpose of the invention is to provide the application of the hot melt pressure sensitive adhesive in bonding materials such as plastics, metals, fibers, leatherware and the like.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the maleic anhydride grafted polyolefin wax is mainly prepared from the following raw materials in parts by weight:
85-90 parts of metallocene polyolefin wax,
1-6 parts of maleic anhydride,
0.1 to 0.8 portion of initiator,
5-15 parts of a plasticizer,
0 to 1 part of an antioxidant, wherein,
and 0.5-2 parts of active auxiliary monomer.
According to the maleic anhydride grafted polyolefin wax, the active auxiliary monomer is adopted, and the high reaction activity of the auxiliary monomer is utilized, so that redundant free radicals cannot attack molecular chains of the metallocene polyolefin wax in the reaction process, the cracking of β chains in the molecular chains of the polyolefin wax in the grafting process is reduced, and the stability of the molecular chains of the polypropylene wax is improved.
The maleic anhydride grafted polyolefin wax prepared by the substances has good high-temperature fluidity and strength, has both polar groups and nonpolar groups on a molecular structure, can be used as an interface compatilizer for hot-melt pressure-sensitive adhesives, and can remarkably improve the processing fluidity, compatibility and bonding strength of the hot-melt pressure-sensitive adhesives.
In addition, the invention adopts a certain amount of plasticizer, which can dilute the initiator, so that the grafting reaction is more stable and uniform, the generation of side reaction is further reduced, and the adverse effect of subsequent reduction of the surface viscosity of the hot-melt pressure-sensitive adhesive is also avoided.
In a particular embodiment of the invention, the reactive auxiliary monomer comprises a monomer containing a carbon-carbon double bond.
In a preferred embodiment of the present invention, the reactive auxiliary monomer comprises any one or more of a styrene monomer, a (meth) acrylate monomer, and an unsaturated carboxylic acid monomer.
In the present invention, the (meth) acrylate refers to a methacrylate or an acrylate.
The (meth) acrylate-based monomer includes any one or more of a (meth) acrylate and a substituted (meth) acrylate. Substituted (meth) acrylates are those substituted on the ester group, and the substituents may be selected from alkyl, hydroxy, alkoxy, and the like.
In the embodiment of the present invention, it is further preferable that the reactive auxiliary monomer is an alkoxylated (meth) acrylate monomer.
The invention adopts the alkoxylated (methyl) acrylate monomer, has high activity, high boiling point and low irritation, can improve the grafting rate of polar groups, reduces the cracking of β chains in polyolefin wax molecular chains in the grafting process, and improves the stability of the polyolefin wax molecular chains.
In a specific embodiment of the present invention, the alkoxylated (meth) acrylate monomers include one or more of propoxylated neopentyl glycol diacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated neopentyl glycol methoxy monoacrylate, 1, 6-hexanediol methoxy monoacrylate, glycerol methoxy monoacrylate.
As in various embodiments, the reactive auxiliary monomer may be used in amounts of 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, and the like.
In a specific embodiment of the present invention, the metallocene polyolefin wax has a number average molecular weight of 500 to 10000, and a ring and ball softening point of 100 to 160 ℃.
The metallocene polyolefin wax has narrow molecular weight distribution, better molecular structure stability and better thermal stability. Metallocene polyolefin waxes are polyolefin waxes prepared in the presence of a metallocene as catalyst.
In a particular embodiment of the invention, the metallocene polyolefin wax comprises a metallocene polyethylene wax and/or a metallocene polypropylene wax. Preferably, the metallocene polyolefin wax is a metallocene polypropylene wax. The maleic anhydride grafted polypropylene wax prepared from the metallocene polypropylene wax is used for hot melt pressure sensitive adhesive and can further improve the bonding property.
In a specific embodiment of the invention, the number average molecular weight of the metallocene polypropylene wax is 500-6000, and the ring and ball softening point of the metallocene polypropylene wax is 135-155 ℃.
As in the various embodiments, the metallocene polyolefin wax may be used in amounts of 85 parts, 85.5 parts, 86 parts, 86.5 parts, 87 parts, 87.5 parts, 88 parts, 88.5 parts, 89 parts, 89.5 parts, 90 parts, and the like.
In a particular embodiment of the invention, the initiator is a free radical initiator.
In a particular embodiment of the invention, the free radical initiator comprises a peroxide initiator.
In a specific embodiment of the invention, the peroxide initiator comprises one or more of di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, bis (tert-butylperoxyisopropyl) benzene, tert-butylcumyl peroxide.
As in the various embodiments, the initiator may be used in amounts of 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, and the like.
In a particular embodiment of the invention, the plasticizer comprises naphthenic and/or paraffinic oil.
The plasticizer of the invention is used for diluting the initiator, so that the grafting reaction is more stable and uniform, and the generation of side reaction is reduced. In addition, the invention adopts mineral oil as a plasticizer, so that the volatilization is avoided, the environmental protection property is good, and the prepared maleic anhydride grafted polyolefin wax modifies the hot-melt pressure-sensitive adhesive, thereby avoiding the adverse effect of reducing the surface viscosity of the hot-melt pressure-sensitive adhesive.
As in various embodiments, the plasticizer may be used in amounts of 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, and the like.
In a specific embodiment of the present invention, an antioxidant is further included. Specifically, the using amount of the antioxidant is 0.001-1 part.
As in various embodiments, the antioxidant may be used in amounts of 0.001 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, and the like. The dosage of the antioxidant can be selected according to the actual application condition, and the antioxidant can also not be added.
In a specific embodiment of the present invention, the antioxidant includes any one or more of hindered phenol type antioxidants, phosphite type antioxidants, and thiodipropyl ester type antioxidants.
Specifically, the hindered phenol antioxidant comprises pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, the phosphite antioxidant comprises tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenyl) pentaerythritol tetraalcohol diphosphite, and the thiodipropyl antioxidant comprises pentaerythrityl dodecathiopropyl and/or distearyl thiodipropionate.
The maleic anhydride used in the present invention may be a colorless plate crystal.
As in various embodiments, the maleic anhydride can be used in amounts of 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, and the like.
The invention also provides a preparation method of the maleic anhydride grafted polyolefin wax, which is prepared by a melt grafting method.
In a specific embodiment of the present invention, the preparation method comprises the steps of:
and uniformly mixing the metallocene polyolefin wax, the maleic anhydride, the active auxiliary monomer and the antioxidant at 140-170 ℃, reacting for 1-2 h under the action of the initiator premixed in the plasticizer, and removing unreacted raw materials under reduced pressure.
According to the maleic anhydride grafted polyolefin wax, the active auxiliary monomer in the raw materials improves the overall reaction activity, so that the reaction is smoothly carried out at the temperature of 140-170 ℃, side reactions are reduced, and the molecular chain of the polyolefin wax is more stable.
In a specific embodiment of the present invention, the initiator premixed in the plasticizer is added dropwise.
In a specific embodiment of the present invention, the method for removing unreacted monomers comprises: stirring for 1-2 h under the condition of reduced pressure and heating, and vacuumizing the reaction system by a vacuum pump.
The invention also provides a hot-melt pressure-sensitive adhesive which comprises 2 to 10 weight percent of maleic anhydride grafted polyolefin wax.
In a specific embodiment of the invention, the hot melt pressure sensitive adhesive comprises the following components in parts by weight:
10-40 parts of a thermoplastic elastomer,
10-35 parts of a plasticizer,
40-65 parts of tackifying resin,
0 to 1 part of an antioxidant, wherein,
and 2-10 parts of maleic anhydride grafted polyolefin wax;
the maleic anhydride-grafted polyolefin wax is any one of the maleic anhydride-grafted polyolefin waxes mentioned above.
The specific maleic anhydride grafted polyolefin wax has high grafting rate of polar groups, and meanwhile, the polyolefin wax has good molecular chain stability, and has both polar groups and nonpolar groups on the molecular structure, so that the compatibility of the hot-melt pressure-sensitive adhesive can be remarkably improved by using the polyolefin wax as an interface compatilizer; meanwhile, the hot-melt pressure-sensitive adhesive modified by maleic anhydride grafted polyolefin wax has good processing fluidity, obviously enhances the peeling strength of the base material, slightly increases the annular initial adhesion, breaks through the bonding limitation of the hot-melt pressure-sensitive adhesive, widens the application range of the hot-melt pressure-sensitive adhesive, and can be widely used for bonding materials such as plastics, metals, fibers, leatherware and the like.
As in various embodiments, the maleic anhydride-grafted polyolefin wax may be used in amounts of 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, and the like.
In a particular embodiment of the invention, the thermoplastic elastomer comprises a styrenic thermoplastic elastomer. Preferably, the styrene block content in the thermoplastic elastomer is 14 to 45% by weight. Further, in the thermoplastic elastomer, the diblock content may be 0% to 70% by weight, and the diblock content may be 0%.
In a specific embodiment of the present invention, the thermoplastic elastomer has a 200 ℃/5kg melt index of 1 to 35 g/min.
In a specific embodiment of the present invention, the thermoplastic elastomer comprises one or more of styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-isoprene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS) and modified derivatives thereof.
Wherein, the respective modified derivatives of the thermoplastic elastomer refer to SIS modified derivatives, SBS modified derivatives, SEBS modified derivatives and SEPS modified derivatives, and the specific modification mode can refer to the conventional modification mode.
In a specific embodiment of the present invention, the plasticizer includes any one or more of naphthenic oil, paraffinic oil, and polybutene. The plasticizer can effectively adjust the thickness and the hardness of the hot-melt pressure-sensitive adhesive so as to meet the actual use requirement.
In a specific embodiment of the present invention, the softening point of the tackifier resin is 80 to 140 ℃.
In a specific embodiment of the present invention, the tackifying resin comprises one or more of rosin resin, terpene phenol resin, carbon five petroleum resin, carbon nine petroleum resin, carbon five carbon nine copolymerized petroleum resin, coumarone resin, polyacrylate resin and modified derivatives thereof.
In a specific embodiment of the present invention, the terpene-phenol resin content in the tackifying resin is 5 wt% to 20 wt%.
As in the specific embodiment, the tackifying resin includes a carbon five carbon nine copolymerized petroleum resin and a terpene phenol resin.
Wherein, the respective modified derivatives of the tackifying resin refer to rosin resin modified derivatives, terpene phenol resin modified derivatives, carbon five petroleum resin modified derivatives, carbon nine petroleum resin modified derivatives, carbon five carbon nine copolymerized petroleum resin modified derivatives, coumarone resin modified derivatives and polyacrylate resin modified derivatives, and the specific modification mode can refer to the conventional modification mode.
In a specific embodiment of the invention, the antioxidant is used in an amount of 0.001 to 1 part.
As in various embodiments, the antioxidant may be used in amounts of 0.001 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, and the like. The dosage of the antioxidant can be selected according to the actual application condition, and the antioxidant can also not be added.
In a specific embodiment of the present invention, the antioxidant includes any one or more of hindered phenol type antioxidants, phosphite type antioxidants, and thiodipropyl ester type antioxidants.
Specifically, the hindered phenol antioxidant comprises pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, the phosphite antioxidant comprises tris (2, 4-di-tert-butylphenyl) phosphite and/or bis (2, 4-di-tert-butylphenyl) pentaerythritol tetraalcohol diphosphite, and the thiodipropyl antioxidant comprises pentaerythrityl dodecathiopropyl and/or distearyl thiodipropionate.
The invention also provides a preparation method of the hot-melt pressure-sensitive adhesive, which comprises the following steps:
and uniformly mixing the plasticizer, the maleic anhydride grafted polyolefin wax, the thermoplastic elastomer and the antioxidant at 140-170 ℃, and then uniformly mixing the mixture with the tackifying resin.
In a specific embodiment of the invention, the plasticizer, the maleic anhydride grafted polyolefin wax, the thermoplastic elastomer and the antioxidant are mixed and stirred at 140-170 ℃, and the mixture is vacuumized for 20-60 min; then mixing and stirring the mixture with the tackifying resin, and vacuumizing for 30-60 min. And (4) after the bubbles are removed, standing for 5-10 min to obtain the hot-melt pressure-sensitive adhesive.
The invention also provides the application of the hot-melt pressure-sensitive adhesive in material bonding, and the hot-melt pressure-sensitive adhesive can be used for bonding plastics, metals, fibers and/or leather products.
As in various embodiments, the hot melt pressure sensitive adhesive can be used to bond a polar substrate Polystyrene (PS) and a non-polar substrate Polyethylene (PE).
Compared with the prior art, the invention has the beneficial effects that:
(1) the maleic anhydride grafted polyolefin wax adopts the active auxiliary monomer, utilizes the high reaction activity thereof, reduces the cracking of β chains in a polyolefin wax molecular chain in the grafting process in the reaction process, and further contributes to improving the stability of the molecular chain of the polypropylene wax;
(2) the maleic anhydride grafted polyolefin wax modified hot-melt pressure-sensitive adhesive has excellent processing mobile phase, obviously enhances the peeling strength of a base material, slightly increases the annular initial adhesion, widens the application range, and can be widely used for bonding materials such as plastics, metals, fibers, leatherware and the like; the hot-melt pressure-sensitive adhesive prepared by the invention has the peeling strength of 33-40N/inch (improved by more than or equal to 30%) for PS, the annular initial adhesion of 24-32N/inch, the peeling strength of 24-28N/inch (improved by more than or equal to 23%) for PE (polyethylene) plates, and the annular initial adhesion of 18-23N/inch.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Some of the raw materials used in the examples of the present invention may be as follows, but are not limited to:
thermoplastic elastomers, styrene-isoprene-styrene (SIS), manufactured by yueyang barren petrochemical limited;
plasticizer, naphthenic oil, manufactured by Guangzhou Dagang Petroleum science and technology Inc.;
tackifying resin, carbon five carbon nine copolymerized petroleum resin, the manufacturer is Ningbo gold Haihesheng photochemical Co., Ltd; pentaerythritol rosin ester, manufactured by guangdong science maolin chemical limited; terpene phenol resin, manufactured by Guangxi Sterculia Chondra chemical industry Co., Ltd;
antioxidant, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF, Germany, tris (2, 4-di-tert-butylphenyl) phosphite, manufactured by BASF, Germany;
metallocene polyolefin waxes, metallocene polypropylene waxes, manufactured by Clariant, switzerland;
maleic anhydride, manufactured by Mimi European Chemicals Co., Tianjin;
initiator, di-t-butyl peroxide (DTBP), available from Aksunobell, Netherlands;
the activated auxiliary monomer, glycerol methoxyl monoacrylate, is produced by Shanghai Demao chemical Co.
Maleic anhydride grafted SEBS is commercially available from Kraton, USA.
Example 1
This example provides a maleic anhydride grafted polyolefin wax made from the following raw materials in parts by weight:
85 parts of metallocene polypropylene wax, 3.7 parts of maleic anhydride, 1.0 part of glycerol methoxy monoacrylate, 0.3 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.2 part of tris (2, 4-di-tert-butylphenyl) phosphite, 0.3 part of di-tert-butyl peroxide and 10 parts of naphthenic oil.
The preparation method of maleic anhydride-grafted polyolefin wax of this example comprises the following steps:
(1) 0.3 part of di-tert-butyl peroxide and 10 parts of naphthenic oil are mixed uniformly in advance;
(2) heating a stirring kettle to 155 ℃, adding 85 parts of metallocene polypropylene wax, 3.7 parts of maleic anhydride, 1.0 part of glycerol methoxy monoacrylate, 0.3 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.2 part of tris (2, 4-di-tert-butylphenyl) phosphite into the stirring kettle, stirring and melting, and dropwise adding the mixture obtained in the step (1) into the stirring kettle;
(3) after the dropwise adding in the step (2) is finished, continuously reacting for 1.5h, and stirring at the rotating speed of 30-100 r/min; and then slowly stirring for 1.5h at the rotating speed of 10-25 r/min under the vacuum-pumping condition, and decompressing and pumping out unreacted maleic anhydride and glycerol methoxyl monoacrylate to obtain maleic anhydride grafted polypropylene wax 1 #.
Example 2
This example provides a maleic anhydride grafted polyolefin wax made from the following raw materials in parts by weight:
85.5 parts of metallocene polypropylene wax, 3.7 parts of maleic anhydride, 0.5 part of glycerol methoxy monoacrylate, 0.3 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.2 part of tris (2, 4-di-tert-butylphenyl) phosphite, 0.3 part of di-tert-butyl peroxide and 10 parts of naphthenic oil.
The preparation method of maleic anhydride-grafted polyolefin wax of this example comprises the following steps:
(1) 0.3 part of di-tert-butyl peroxide and 10 parts of naphthenic oil are mixed uniformly in advance;
(2) heating a stirring kettle to 155 ℃, adding 85 parts of metallocene polypropylene wax, 3.7 parts of maleic anhydride, 0.5 part of glycerol methoxy monoacrylate, 0.3 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.2 part of tris (2, 4-di-tert-butylphenyl) phosphite into the stirring kettle, stirring and melting, and dropwise adding the mixture obtained in the step (1) into the stirring kettle;
(3) after the dropwise adding in the step (2) is finished, continuously reacting for 1.5h, and stirring at the rotating speed of 30-100 r/min; and then slowly stirring for 1.5h at the rotating speed of 10-25 r/min under the vacuum-pumping condition, and decompressing and pumping out unreacted maleic anhydride and glycerol methoxyl monoacrylate to obtain maleic anhydride grafted polypropylene wax 2 #.
Example 3
This example refers to the maleic anhydride-grafted polyolefin wax of example 1 and the process for its preparation, with the only difference that:
1.0 part of glycerol methoxyl monoacrylate is replaced by 1.0 part of styrene to obtain maleic anhydride grafted polypropylene wax 3 #. In the preparation process, the irritant styrene monomer is easy to volatilize, and the obtained maleic anhydride grafted polypropylene wax No. 3 product has relatively large smell and irritation.
Examples 4 to 8
This example provides a hot melt pressure sensitive adhesive, which is prepared from the following components in parts by weight, with specific components and amounts shown in table 1.
TABLE 1 Components and amounts of different hot-melt pressure-sensitive adhesives
The preparation method of the hot melt pressure sensitive adhesive of the embodiment comprises the following steps:
heating the stirring kettle to 160 ℃, adding the thickening agent, the antioxidant (if the raw material components contain no antioxidant, the antioxidant is not added), the thermoplastic elastomer and the maleic anhydride grafted polyolefin wax into the stirring kettle, mixing and stirring, vacuumizing for about 40min until the mixture is completely melted, adding the tackifying resin, continuing vacuumizing and stirring for 60min, removing bubbles, and standing for 5min to obtain the hot-melt pressure-sensitive adhesive.
Comparative examples 1 to 3
Comparative examples 1-3 provide hot melt pressure sensitive adhesives made from the following ingredients in parts by weight, with specific ingredients and amounts as shown in table 2.
TABLE 2 Components and amounts of different hot-melt pressure-sensitive adhesives
The preparation method of the hot melt pressure sensitive adhesive of the comparative example refers to examples 4 to 8.
The maleic anhydride grafted polyolefin wax 3# is mainly prepared from the following raw materials in parts by weight:
86 parts of metallocene polypropylene wax, 3.7 parts of maleic anhydride, 0.3 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.2 part of tris (2, 4-di-tert-butylphenyl) phosphite, 0.3 part of di-tert-butyl peroxide and 10 parts of naphthenic oil.
Preparation of maleic anhydride-grafted polyolefin wax # 3 reference was made to the preparation of example 1.
Experimental example 1
In order to illustrate the effects of different hot melt adhesives by comparison, the properties of the hot melt pressure sensitive adhesives of examples 4 to 8 and comparative examples 1 to 3 were tested, and the test results are shown in table 3.
TABLE 3 Performance test results for different hot-melt pressure-sensitive adhesives
The method for testing the thin consistency refers to GB/T2794, the method for testing the peel strength refers to GB/T2792, and the method for testing the annular initial adhesion refers to GB/T31125.
Comparative example 3, example 4, example 6 and example 7 correspond to the following parts of the maleic anhydride grafted polypropylene wax 1# in the hot melt pressure sensitive adhesive, respectively, in the amounts of 0 part, 6 parts, 3 parts and 9 parts, and the test results show that: the maleic anhydride grafted polypropylene wax modified hot-melt pressure-sensitive adhesive has the advantages of reduced thickness, better fluidity, and improved peel strength of 24-29N/inch (improved by more than or equal to 23% compared with comparative example 3) for polar base material PS plates to 33-40N/inch (improved by more than or equal to 30% compared with comparative example 3), and slightly improved annular initial adhesion for two base materials.
The difference between the embodiment 4 and the embodiment 5 and the comparative embodiment 1 is that maleic anhydride grafted polypropylene wax with different addition amounts of the active monomers 1#, 2# and 3#, and the test result shows that the thinner the consistency of the prepared maleic anhydride grafted polypropylene wax modified hot melt pressure sensitive adhesive is, the lower the degradation side reaction of the polypropylene is effectively reduced by the active monomers. The peel strength and loop shape of the hot melt pressure sensitive adhesive also decrease.
The difference between example 4 and example 8 is that a part of terpene-phenol resin is added in example 8, and the test result shows that the addition of terpene-phenol resin increases the peeling strength, but reduces the ring tack, and the actual selection can be made according to the application scene.
The difference between comparative example 2 and example 4 is that the commercially available maleic anhydride grafted SEBS is adopted to modify the hot-melt pressure-sensitive adhesive in comparative example 2, and the test result shows that compared with the maleic anhydride grafted polypropylene wax of the present invention, the maleic anhydride grafted SEBS can significantly increase the thin consistency of the hot-melt pressure-sensitive adhesive, is not favorable for high temperature fluidity and processability, slightly improves the peel strength, but has no similar effect as the maleic anhydride grafted polypropylene wax of the present invention, and the ring initial adhesion is significantly reduced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The maleic anhydride grafted polyolefin wax is characterized by being mainly prepared from the following raw materials in parts by weight:
85-90 parts of metallocene polyolefin wax,
1-6 parts of maleic anhydride,
0.1 to 0.8 portion of initiator,
5-15 parts of a plasticizer,
0 to 1 part of an antioxidant, wherein,
and 0.5-2 parts of active auxiliary monomer.
2. The maleic anhydride-grafted polyolefin wax according to claim 1, wherein the reactive auxiliary monomer comprises a monomer containing a carbon-carbon double bond;
preferably, the active auxiliary monomer comprises any one or more of styrene monomers, (methyl) acrylate monomers and unsaturated carboxylic acid monomers;
preferably, the (meth) acrylate monomer is an alkoxylated (meth) acrylate monomer;
more preferably, the alkoxylated (meth) acrylate monomers include one or more of propoxylated neopentyl glycol diacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated neopentyl glycol methoxy monoacrylate, 1, 6-hexanediol methoxy monoacrylate, glycerol methoxy monoacrylate.
3. Maleic anhydride-grafted polyolefin wax according to claim 1 or 2, wherein the metallocene polyolefin wax has a number average molecular weight of 500 to 10000;
preferably, the ring and ball softening point of the metallocene polyolefin wax is 100-160 ℃;
optionally, the metallocene polyolefin wax comprises a metallocene polyethylene wax and/or a metallocene polypropylene wax;
preferably, the metallocene polyolefin wax is metallocene polypropylene wax, the number average molecular weight of the metallocene polypropylene wax is 500-6000, and the ring and ball softening point of the metallocene polypropylene wax is 135-155 ℃.
4. Maleic anhydride-grafted polyolefin wax according to claim 1 or 2, characterized in that the initiator is a free radical initiator;
optionally, the free radical initiator comprises a peroxide initiator;
optionally, the peroxide initiator comprises one or more of di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, bis (tert-butylperoxyisopropyl) benzene, tert-butylcumyl peroxide;
preferably, the plasticizer comprises naphthenic oil and/or paraffinic oil;
preferably, the using amount of the antioxidant is 0.001-1 part.
5. A process for the preparation of maleic anhydride-grafted polyolefin waxes according to any of claims 1 to 4, comprising the steps of:
and uniformly mixing the metallocene polyolefin wax, the maleic anhydride, the active auxiliary monomer and the antioxidant at 140-170 ℃, reacting for 1-2 h under the action of the initiator premixed in the plasticizer, and removing unreacted raw materials under reduced pressure.
6. A hot-melt pressure-sensitive adhesive comprising the maleic anhydride-grafted polyolefin wax according to any one of claims 1 to 4;
preferably, the mass of the maleic anhydride grafted polyolefin wax is 2 to 10 percent of the mass of the hot melt pressure sensitive adhesive.
7. The hot-melt pressure-sensitive adhesive according to claim 6, comprising the following components in parts by weight:
10-40 parts of a thermoplastic elastomer,
10-35 parts of a plasticizer,
40-65 parts of tackifying resin,
0 to 1 part of an antioxidant, wherein,
and 2-10 parts of maleic anhydride grafted polyolefin wax;
preferably, the thermoplastic elastomer comprises a styrenic thermoplastic elastomer;
more preferably, in the thermoplastic elastomer, the content of the styrene block is 14 to 45% by weight;
preferably, the melt index of the thermoplastic elastomer at 200 ℃/5kg is 1-35 g/min;
optionally, the thermoplastic elastomer includes one or more of a styrene-isoprene-styrene block copolymer, a styrene-butadiene-isoprene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, and modified derivatives thereof.
8. The hot melt pressure sensitive adhesive of claim 7, wherein the plasticizer comprises any one or more of naphthenic oil, paraffinic oil, and polybutene;
optionally, the softening point of the tackifying resin is 80-140 ℃;
optionally, the tackifying resin comprises one or more of rosin resin, terpene phenol resin, carbon five petroleum resin, carbon nine petroleum resin, carbon five carbon nine copolymerized petroleum resin, coumarone resin, polyacrylate resin and respective modified derivatives;
optionally, the amount of the antioxidant is 0.001-1 part.
9. A process for preparing a hot melt pressure sensitive adhesive according to claim 7 or 8, comprising the steps of:
and uniformly mixing the plasticizer, the maleic anhydride grafted polyolefin wax, the thermoplastic elastomer and the antioxidant at 140-170 ℃, and then uniformly mixing the mixture with the tackifying resin.
10. Use of the hot melt pressure sensitive adhesive according to any one of claims 6 to 8 for material bonding;
preferably, the material comprises plastic, metal, fiber and/or leather.
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| CN202010286850.8A CN111440271A (en) | 2020-04-13 | 2020-04-13 | Maleic anhydride grafted polyolefin wax, hot-melt pressure-sensitive adhesive modified by using same, and preparation method and application of hot-melt pressure-sensitive adhesive |
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